CN1271029C - Preparation of benzaldehyde and substituted benzaldehyde by circulation phase transfer catalytic hydrolysis method - Google Patents
Preparation of benzaldehyde and substituted benzaldehyde by circulation phase transfer catalytic hydrolysis method Download PDFInfo
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- CN1271029C CN1271029C CN200410041631.4A CN200410041631A CN1271029C CN 1271029 C CN1271029 C CN 1271029C CN 200410041631 A CN200410041631 A CN 200410041631A CN 1271029 C CN1271029 C CN 1271029C
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- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title description 3
- 150000003935 benzaldehydes Chemical class 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 benzal Chemical class 0.000 claims abstract description 48
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000003408 phase transfer catalysis Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical class 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- HNJXPTMEWIVQQM-UHFFFAOYSA-M triethyl(hexadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC HNJXPTMEWIVQQM-UHFFFAOYSA-M 0.000 claims description 2
- BMHBMLLQKJESDS-UHFFFAOYSA-N benzene;formaldehyde Chemical class O=C.C1=CC=CC=C1 BMHBMLLQKJESDS-UHFFFAOYSA-N 0.000 claims 8
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 claims 5
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 5
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 4
- 229940073608 benzyl chloride Drugs 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ACNQJGLSENYFQJ-UHFFFAOYSA-N 1-chloro-3-(dichloromethyl)benzene Chemical compound ClC(Cl)C1=CC=CC(Cl)=C1 ACNQJGLSENYFQJ-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229940077935 zinc phosphate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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Abstract
The invention relates to a method for preparing a compound which can be expressed as G by adopting a circulating hydrolysis method6H(5-n)XnA process for preparing aromatic aldehyde from CHO (n is 0, 1, 2, X can be hydrogen atom, halogen atom, trifluoromethyl, etc.) includes such steps as hydrolyzing benzal chloride or substituted benzal chloride in the presence of water by phase transfer catalyst in the mass ratio of 1-15: 1, and determining the initial addition of catalyst in the range of 0.1-10 wt% of benzal chloride or substituted benzal chlorideThe reaction is carried out at the temperature of 60-110 ℃; the water phase after the hydrolysis reaction can be recycled for the next hydrolysis reaction, and only the water consumed by the previous hydrolysis is replenished in the next hydrolysis reaction.
Description
Technical field
The present invention relates to the synthetic of organic compound, say so in more detail and adopt the preparation of recirculated water solution to can be expressed as C
6H
(5-n)X
nCHO (n=0,1,2.X can be hydrogen atom, halogen atom, trifluoromethyl etc.) the aromatic aldehyde novel process.Belong to chemical manufacturing field.
Background technology
Phenyl aldehyde is the important organic intermediate that is widely used in medicine, agricultural chemicals, spices etc. with containing the substituting group phenyl aldehyde.Phenyl aldehyde or the synthetic method that contains the substituting group phenyl aldehyde mainly contain with toluene or contain oxidation style and chlorinolysis and the benzylidene chloride that substituting group toluene is raw material or contain substituent benzylidene chloride catalytic hydrolysis method.
Oxidation style mainly contains vapour phase oxidation process, liquid phase oxidation and electrochemical oxidation process, and gaseous oxidation and liquid phase oxidation are that raw material gets with oxygen or atmospheric oxidation with toluene or replacement toluene.Patent CN1031819C announced a kind of on the load catalyzer of vanadium, silver, nickel the method for gas phase oxidation of toluene producing benzaldehyde, the selectivity of phenyl aldehyde has only 60%, once through yield only 16%.The primary product that the liquid-phase oxidation of toluene or replacement toluene obtains is corresponding phenylformic acid or substituted benzoic acid, liquid-phase oxidation patent CN1113835 has announced with cobalt salt and manganese salt to be the method for high added values such as the acquisition phenyl aldehyde of method maximum possible of toluene liquid-phase oxidation of catalyzer and phenylcarbinol, the productive rate of phenyl aldehyde also can only reach product or the phenylformic acid more than 20%, 60%.Therefore with toluene or to contain substituting group toluene be that feedstock production phenyl aldehyde or the gaseous oxidation that contains the substituting group phenyl aldehyde and liquid-phase oxidation all exist the shortcoming that yield is low, by product is many, separating technology is complicated.Adopt this class methods mass preparation phenyl aldehyde or contain the substituting group phenyl aldehyde, just must build more massive phenylformic acid or contain the benzoic full scale plant of substituting group.Electrochemical oxidation method is still under test, and is remoter apart from industrialization.
Chlorinolysis is with toluene or contains the substituting group Benzyl Side-Chain Chloride gained muriate phenyl aldehyde that hydrolysis obtains under catalyst action or contain the substituting group phenyl aldehyde, with toluene or contain the yield that substituting group toluene calculates and have only 50%.
Benzylidene chloride or contain the existing report of the catalytic hydrolysis (GB899953 of substituting group benzylidene chloride, US3087967, US3524885, US4229379, US5347054), hydrolyst is selected soluble zinc salt, as zinc chloride, zinc phosphate, zinc sulfate and zinc bromide etc., phenyl aldehyde or the yield that contains the substituting group phenyl aldehyde be all more than 95%, but zinc salt catalyzer easy inactivation in excessive water, influence quality product, serious is the heavy metal contamination that has caused environment.Patent US4229379 adopts concentrated hydrochloric acid to make catalyzer, the yield of phenyl aldehyde can reach 98%, and reacts HCl gas reusable edible after packing tower absorbs of emitting, but water consumption is bigger, reach 10～25 times of stoichiometric number, the capacity utilization of reactor is little.
In sum, with toluene or contain oxidation style that substituting group toluene is raw material and chlorinolysis and produce phenyl aldehyde or contain the substituting group phenyl aldehyde and have selectivity and the low defective of yield.Existing with benzylidene chloride or to replace benzylidene chloride be problems such as the catalytic hydrolysis method of raw material exists heavy metal contamination, poor product quality and the water consumption of catalyzer big, the reactor volume utilization ratio is low.
Summary of the invention
The purpose of this invention is to provide a kind of with benzylidene chloride or to contain the substituting group benzylidene chloride be raw material production phenyl aldehyde or the circulation phase-transfer catalysis hydrolysis method that contains the substituting group phenyl aldehyde, the process for cleanly preparing that promptly adopts phase-transfer catalyst and hydrolysis process water cycle to use.
Purpose of the present invention can reach by following measure:
A kind of circulation phase-transfer catalysis hydrolysis method prepares phenyl aldehyde or contains the substituting group phenyl aldehyde, it is characterized in that with benzylidene chloride or to contain the substituting group benzylidene chloride be raw material, in the presence of water, adopts the phase-transfer catalyst reaction that is hydrolyzed.Because reactant and product are all water insoluble, catalyzer should have the phase-transfer catalysis performance, to increase the collision opportunity of reactant and water.And catalyzer has water-soluble, can recycle with process water.It is R that the present invention adopts general formula
3N
R ' X
Quaternary ammonium salt-type phase transfer catalyst, wherein R ' is the alkyl or the benzyl of 1～16 carbonatoms, R is the alkyl of 1～4 carbonatoms, X is fluorine, chlorine, bromine atoms, for example benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl trimethyl Neutral ammonium fluoride, palmityl trimethyl ammonium chloride, cetyltriethylammonium bromide, tetrabutylammonium chloride, Tetrabutyl amonium bromide and etamon chloride etc.Water and benzylidene chloride or the addition that contains the substituting group benzylidene chloride are generally by mass ratio 1～15: 1 control, and the stoichiometric relation of pressing hydrolysis reaction, water is to benzylidene chloride or to contain the substituting group benzylidene chloride excessive, and be good at preferred 2～5: 1.The initial add-on of catalyzer can or contain in 0.1～10% scope of substituting group benzylidene chloride weight at benzylidene chloride determines that preferred 0.5～2.5% is good.Reaction generally can be carried out in 60～110 ℃ of temperature ranges, and preferred 95～105 ℃ is good.
Preparation method of the present invention is at benzylidene chloride or after containing the substituting group benzylidene chloride and reacting completely, the reaction solution standing demix, and organic phase contains desired product, through with the less water washing, can get highly purified product again after fractionation.Aqueous phase contains catalyzer, and water is limpid in sight transparent, and can directly circulate is used for hydrolysis reaction next time.The water yield that hydrolysis is next time only added last hydrolysis reaction and consumed, the water of adding can be the used less water of above-mentioned washing.Can not add catalyzer or only add little amount of catalyst, can form the closed cycle of hydrolysis water and catalyzer like this.Phenyl aldehyde or the yield that contains the substituting group phenyl aldehyde surpass 98%.The HCl gas that hydrolytic process discharges can by-product hydrochloric acid through falling film absorption.Whole hydrolysis reaction does not all have waste water, waste gas and waste residue outwards to discharge, and is process for cleanly preparing.
Manufacture method of the present invention can adopt two kinds of interrupter method and continuous processings.Interrupter method is with benzylidene chloride or contain substituting group benzylidene chloride, water and catalyzer adds in the reactor, reacts under certain temperature and agitation condition.After reaction is finished, standing demix, the organic phase that obtains can get high purity product after underpressure distillation.The water circulation that obtains after leaving standstill is used for next hydrolysis reaction.
Continuous processing can adopt two kinds of forms of tower or many still series connection.Adopt tower continuous hydrolysis technology, benzylidene chloride or contain substituting group benzylidene chloride, water and catalyzer and at the bottom of tower, add continuously with certain proportion, in tower under the effect of internals or weighting material, after the living catalytic hydrolysis reaction of sufficient contact hybrid concurrency, reaction solution is discharged from cat head, pass through phase splitter then, the organic phase that obtains thus can get purity greater than 99.5% product after underpressure distillation.The water that obtains from phase splitter returns at the bottom of the tower.Adopt the placed in-line continuous hydrolysis technology of many stills, benzylidene chloride or contain substituting group benzylidene chloride, water and catalyzer joins in first hydrolytic reaction pot that has agitator simultaneously continuously, successively from a last reactor overflow to next reactor, benzylidene chloride or to contain substituting group benzylidene chloride primitive reaction complete when leaving last reactor, enter phase splitter, the organic phase that obtains is a product more than 99.5% through getting purity after the underpressure distillation.The water that obtains from phase splitter returns first hydrolytic reaction pot.The platform number of hydrolytic reaction pot generally can be in 3～6 scopes, and preferred 4～5 is good.
Description of drawings
Fig. 1 is phenyl aldehyde of the present invention or the process flow sheet that contains substituting group phenyl aldehyde circulation catalytic hydrolysis production process.
Embodiment
Further describe the present invention below in conjunction with embodiment.
Embodiment 1:
In the flat three neck reactors of the 500ml that has magnetic agitation, add (the self-control of 50g benzylidene chloride respectively, purity 99%), weight is that water and the weight of m1 are the benzyltriethylammoinium chloride of m2, control certain reaction temperature T 1 was reacted until benzylidene chloride in stirring reaction t1 minute.The reaction solution standing demix obtains organic phase and water respectively.Organic match weight m3, and use the gas chromatography determination area percent, calculate the quality percentage composition x of phenyl aldehyde.Test-results is referring to table 1.
Table 1
| No. | m1 | m2 | T1 | t1 | m3 | X |
| [g] | [g] | [℃] | [min] | [g] | [％] | |
| 1 | 80 | 0.1 | 90 | 240 | 32.9 | 99.3 |
| 2 | 80 | 0.1 | 100 | 200 | 32.8 | 99.5 |
| 3 | 80 | 0.1 | 110 | 180 | 32.9 | 99.5 |
| 4 | 60 | 0.1 | 100 | 280 | 33.0 | 99.1 |
| 5 | 100 | 0.1 | 100 | 180 | 32.8 | 99.4 |
| 6 * | 0 | 0 | 100 | 200 | 32.9 | 99.3 |
| 7 * | 0 | 0 | 100 | 200 | 33.0 | 99.2 |
| 8 * | 0 | 0 | 100 | 200 | 32.7 | 99.3 |
| 9 * | 0 | 0 | 100 | 200 | 32.9 | 99.1 |
*In experiment 6-9, all use from the water of testing 2 reaction solution to recycle, do not add water and catalyzer.
Embodiment 2:
In the flat three neck reactors of the 500ml that has magnetic agitation, add 50g respectively benzyl chloride is pitched dichloro (self-control, purity 99%), weight is that water and the weight of m1 are the etamon chloride of m2, control certain reaction temperature T 1, stirring reaction t1 minute until benzyl chloride fork dichloro has been reacted.Reaction solution insulation standing demix obtains organic phase and water respectively.Organic match weight m3, and use the gas chromatography determination area percent, calculate the quality percentage composition x of 4-chloro-benzaldehyde.Test-results is referring to table 2.
Table 2
| No. | ml | m2 | T1 | t1 | m3 | X |
| [g] | [g] | [℃] | [min] | [g] | [％] | |
| 1 | 80 | 0.1 | 90 | 500 | 35.9 | 99.1 |
| 2 | 80 | 0.1 | 100 | 450 | 35.9 | 99.1 |
| 3 | 80 | 0.2 | 100 | 450 | 35.8 | 99.3 |
| 4 | 100 | 0.1 | 100 | 380 | 35.8 | 99.2 |
| 5 | 120 | 0.1 | 100 | 260 | 35.8 | 99.2 |
| 6 * | 140 | 0.1 | 100 | 260 | 35.8 | 99.3 |
| 7 * | 0 | 0 | 100 | 400 | 35.9 | 99.1 |
| 8 * | 0 | 0 | 100 | 400 | 35.9 | 99.1 |
| 9 * | 0 | 0 | 100 | 400 | 35.8 | 99.1 |
*In experiment 7-9, all use from the water of testing 5 reaction solution to recycle, do not add water and catalyzer.
Embodiment 3:
In the flat three neck reactors of the 500ml that has magnetic agitation, add (the self-control of the adjacent benzyl chloride fork of 50g dichloro respectively, purity 99%), weight is that water and the weight of m1 are the tetrabutylammonium chloride of m2, control certain reaction temperature T 1 was pitched dichloro until adjacent benzyl chloride and has been reacted in stirring reaction t1 minute.The reaction solution standing demix obtains organic phase and water respectively.Organic match weight m3, and use the gas chromatography determination area percent, calculate the quality percentage composition x of o-chlorobenzaldehyde.Test-results is referring to table 3.
Table 3
| No. | m1 | m2 | T1 | t1 | m3 | X |
| [g] | [g] | [℃] | [min] | [g] | [％] | |
| 1 | 120 | 0.5 | 100 | 1200 | 35.9 | 99.0 |
| 2 | 120 | 1.5 | 100 | 1100 | 35.9 | 99.1 |
| 3 | 120 | 2.5 | 100 | 900 | 35.8 | 99.3 |
Embodiment 4:
In 500 milliliters that have magnetic agitation flat three neck reactors, add 50 gram m-chloro benzylidene chloride (self-controls respectively, purity 99%), the Tetrabutyl amonium bromide of the water of 160 grams and 0.5 gram, 100 ℃ of control reaction temperature, stirring reaction 70 hours. the reaction solution standing demix obtains organic phase and water respectively.Organic match weight 35.6 gram, and use the gas chromatography determination area percent, the quality percentage composition of calculating m chlorobenzaldehyde is 99%.
Embodiment 5:
(the industrial toluene chlorination makes to add 700 kilograms benzylidene chloride in 3000 liters built-in churned mechanically chuck enamel still, purity 99%), the benzyltriethylammoinium chloride of 1400 kilograms water and 3.5 kilograms, adopt water vapor to be heated to 95 ℃ of still temperature, the vapour phase that reaction produces is through the graphite condenser condensation, the liquid-phase reflux that cools down is to reactor, and the hydrogen chloride gas gas phase that is not condensed enters the tail gas absorption system.Stirring reaction is 4 hours under temperature of reaction, after reaction finishes, stops to stir, and closes heating steam.The reaction solution standing demix, obtain organic match 465 kilograms of weight, and use the gas chromatography determination area percent, the quality percentage composition that calculates phenyl aldehyde is 98.0%, the yield of phenyl aldehyde is 98.3%.The phenyl aldehyde crude product is through obtaining the phenyl aldehyde product of purity more than 99.5% after the underpressure distillation.
Before the underpressure distillation of phenyl aldehyde crude product, divide to add the washing of 80 kg of water for three times, the water of washing back phase-splitting gained is used for replenishing the water of hydrolysis reaction consumes, and uses with the hydrolysis water mixed cycle that last consignment of contains catalyzer.Again add the reaction that is hydrolyzed of 700 kilograms of benzylidene chlorides, through repeated tests, resulting phenyl aldehyde crude product weight is stabilized in 460～470 kilograms of scopes, and content is 97.8～98.5%, and the yield of phenyl aldehyde is between 98～99%.
Embodiment 6:
3000 liters the built-in churned mechanically chuck enamel still series connection that four step ladder types are placed is established graphite condenser on every enamel still.Under the condition of device continous-stable operation, every still all maintains the temperature between 100～105 ℃, stirs.(industrial chlorination toluene makes with benzylidene chloride, purity 99%) be added to first reactor continuously with 600 kilograms/hour flow rate, with the reaction that is hydrolyzed of mixing of materials in the still, then from first reactor overflow to the second successively, the 3rd, the 4th reactor continues reaction, the reaction solution that leaves the 4th reactor enters in the phase splitter 1, the oil phase that phase-splitting obtains enters the washing still, fresh water washing with 70 kilograms/hour, through phase splitter 2 phase-splittings, the oil phase that obtains is the phenyl aldehyde crude product, recording its flow is 395～400 kilograms/hour, the content of analyzing phenyl aldehyde wherein obtains 99.5% phenyl aldehyde product after rectification under vacuum is purified between 98.0～98.5%.The water that obtains from phase splitter 1,2 returns first reactor after mixing, because of the aqueous phase of phase splitter 1 contains catalyzer, do not need to add catalyzer in the production process, or suitably add a spot of catalyzer according to the situation of hydrolysis reaction.The total flow rate of circulation water is about 1500 kilograms/hour, and wherein the content of benzyltriethylammoinium chloride remains on about 0.2%.
Claims (8)
1. a circulation phase-transfer catalysis hydrolysis method prepares phenyl aldehyde or chlorinated benzene formaldehyde, it is characterized in that with benzylidene chloride or chloro benzylidene chloride be raw material, in the presence of water, adopt the phase-transfer catalyst reaction that is hydrolyzed, the addition of water and benzylidene chloride or chloro benzylidene chloride is pressed mass ratio 1～15: 1 control, the initial add-on of catalyzer is determined in 0.1～10% scope of benzylidene chloride or chloro benzylidene chloride weight, is reflected in 60～110 ℃ of temperature ranges and carries out; Water behind the hydrolysis reaction can circulate and be used for next hydrolysis reaction, and the water that last time, hydrolysis was consumed is only added in next hydrolysis.
2. circulation phase-transfer catalysis hydrolysis method according to claim 1 prepares phenyl aldehyde or chlorinated benzene formaldehyde, and it is characterized in that reacting catalyst system therefor is quaternary ammonium salt-type phase transfer catalyst, and its general formula is R
3N
R ' X
, wherein R ' is the alkyl or the benzyl of 1～16 carbonatoms, and R is the alkyl of 1～4 carbonatoms, and X is fluorine, chlorine, bromine atoms.
3. circulation phase-transfer catalysis hydrolysis method according to claim 2 prepares phenyl aldehyde or chlorinated benzene formaldehyde, it is characterized in that quaternary ammonium salt-type phase transfer catalyst is benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl trimethyl Neutral ammonium fluoride, palmityl trimethyl ammonium chloride, cetyltriethylammonium bromide, tetrabutylammonium chloride, Tetrabutyl amonium bromide and etamon chloride.
4. circulation phase-transfer catalysis hydrolysis method according to claim 1 prepares phenyl aldehyde or chlorinated benzene formaldehyde, and the addition that it is characterized in that water and benzylidene chloride or chloro benzylidene chloride is by mass ratio 2～5: 1.
5. circulation phase-transfer catalysis hydrolysis method according to claim 1 prepares phenyl aldehyde or chlorinated benzene formaldehyde, it is characterized in that the initial add-on of catalyzer is definite in 0.5～2.5% scope of benzylidene chloride or chloro benzylidene chloride weight.
6. circulation phase-transfer catalysis hydrolysis method according to claim 1 prepares phenyl aldehyde or chlorinated benzene formaldehyde, it is characterized in that being reflected in 95～105 ℃ of temperature ranges and carries out.
7. circulation phase-transfer catalysis hydrolysis method according to claim 1 prepares phenyl aldehyde or chlorinated benzene formaldehyde, and the phase-transfer catalysis hydrolysis method that it is characterized in that circulating adopts interrupter method or continuous processing production.
8. circulation phase-transfer catalysis hydrolysis method according to claim 7 prepares phenyl aldehyde or chlorinated benzene formaldehyde, it is characterized in that continuous processing adopts tower or two kinds of forms of 4～5 reactor series connection.
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| JP5733055B2 (en) * | 2011-06-29 | 2015-06-10 | 住友化学株式会社 | Method for producing 2- (aryloxymethyl) benzaldehyde compound |
| CN102491887A (en) * | 2011-12-12 | 2012-06-13 | 南京工业大学 | Method for integrated production of benzaldehyde and acyl chloride through benzal chloride acidolysis reaction and hydrolysis reaction |
| CN103396301B (en) * | 2013-07-26 | 2015-09-30 | 扬州天辰精细化工有限公司 | One prepares the method for 2,6-dichlorobenzaldehyde |
| CN106397148A (en) * | 2016-09-12 | 2017-02-15 | 江苏必康制药股份有限公司 | Benzal chloride hydrolysis method |
| CN112047824B (en) * | 2020-08-31 | 2022-04-15 | 中盐常州化工股份有限公司 | Method for producing o/p-chlorobenzaldehyde by low-temperature catalytic oxidation |
| CN112209811A (en) * | 2020-09-14 | 2021-01-12 | 中盐常州化工股份有限公司 | Green low-cost synthesis method of p-hydroxybenzaldehyde |
| CN113429255A (en) * | 2021-06-25 | 2021-09-24 | 常州新东化工发展有限公司 | Continuous production process for co-production of monochlorobenzyl chloride, monochlorobenzaldehyde and monochlorobenzoic acid |
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